Delayed release flavorant compositions

ABSTRACT

Delayed release flavorant compositions containing flavor-release additives, namely 1,2-diols of the formula                    
     wherein R 1  is one of the radicals                    
     where 
     R 2  is H, lower alkyl 
     R 3 , R 4  are H, lower alkyl, lower alkoxy, hydroxy, or R 3 +R 4  together are methylenedioxy, 
     R 5  is lower alkyl 
     and the broken lines represent in the ring one additional bond 
     and in the side chain an optional bond.

This is a divisional of U.S. patent application Ser. No. 08/657,864filed May 31, 1996 now U.S. Pat. No. 5,904,148.

FIELD OF THE INVENTION

The invention concerns delayed release flavorant compositions containing1,2-diols as flavor-release additives.

SUMMARY OF THE INVENTION

The compositions of the invention are selected from the group consistingof

a) smoking compositions e.g. tobacco, and

b) foodstuffs, in particular

b1) bakeable foodstuffs and

b2) microwaveable foodstuffs containing flavor-release additives, namely1,2-diols of the formula

wherein R¹ is one of the radicals

where

R² is H, lower alkyl

R³, R⁴ are H, lower alkyl, lower alkoxy, hydroxy, or R³+R⁴ together aremethylenedioxy,

R⁵ is lower alkyl

and the broken lines represent in the ring one additional bond

and in the side chain an optional bond.

DETAILED DESCRIPTION

The diols I possess no detectable flavor or odor themselves at normaltemperatures and atmospheric conditions but function mainly as flavorprecursors, in as far as they release a flavorant upon heating at highertemperatures, e.g. temperatures leading to pyrolysis and thermolysisrespectively. The diols I thus may be used as flavorants in smokingcompositions, e.g. in tobacco compositions or tobacco substitutes, assustained flavorants and odorants to mask or enhance the flavors andodors of burning tobacco products, and as flavor additives to foods, inparticular bakeable and microwaveable foods.

The term lower alkyl and the alkyl portion of lower alkoxy radicalsuitably refers to straight or branched alkyl residues carrying from 1to 6 carbon atoms. Suitable examples for the individual residues are asfollows:

R² H, CH₃, C₂H₅, etc.

R³, R⁴ H, CH₃, C₂H₅, n- or iso-C₃H₇, t-C₄H₉, etc.

R⁵ CH₃, C₂H₅, n- or iso-C₃H₇, t-C₄H₉, C₅H₁₁, C₆H₁₃, etc.

Although the two radicals R¹ of formula I may be different from eachother and the two radicals R² may also be different from each other, inthe preferred aspects these radicals R¹ and R² respectively are thesame.

As used herein the term “organoleptic” refers to compounds I whichstimulate the sense of smell or taste, and are thus perceived as havinga characteristic odor and/or flavor.

The terms “odor”, “fragrance” and “smell” are used interchangeablywhenever a compound is referred to as an organoleptic which is intendedto stimulate the sense of smell.

The terms “flavor”, “flavoring” and “flavorant” are also usedinterchangeably whenever an organoleptic compound is referred to whichis intended to stimulate the sense of taste.

An “organoleptically effective amount” is a level or amount of thecompounds(s) I present in a material at which the incorporatedcompound(s) exhibit(s) a sensory effect, e.g. by stimulating the senseof smell or taste.

The terms “tobacco” and “tobacco substitutes” are used in theconventional sense and include smokable as well as non-smokable forms inwhich tobacco is regularly used, e.g. cigarettes, snuff, chewablecompositions, etc.

The term “tobacco paper” refers to smokable paper used to containtobacco, e.g. tobacco rolling paper.

The terms “food” and, “foodstuff” are used interchangeably.

The term “food product” would consequently designate the product of theprocess to which the foodstuff(s) containing the diol I is (are)subjected to.

The term “combustible filter” encompasses materials such as naturaltobacco, reconstituted tobacco and tobacco substitutes, etc.

The term “tobacco substitute” is meant to include non-tobacco filledmaterials such as smoking products from sugar beet pulp, coffee beanhulls and other cellulosic or carbohydrate materials, etc.

The preferred compounds I are

1,6-diphenyl-1,5-hexadiene-3,4-diol,

2,5-dihexyl-1,6-diphenyl-1,5-hexadiene-3,4-diol and

1,2-bis(4-hydroxy-3-methoxyphenyl)-1,2-ethanediol.

Further suitable compounds I include

3,4-dimethyl-1,6-bis(2,6,6-trimethyl-1-cyclohexen-1-yl)-1,5-hexadiene-3,4-diol,

3,4-dimethyl-1,6-bis(2,6,6-trimethyl-2-cyclohexen-1-yl)-1,5-hexadiene-3,4-diol,

1,2-bis(1,3-benzodioxol-5-yl)-1,2-ethanediol,

1,2-bis(4-methoxyphenyl)-1,2-ethanediol,

1,2-diphenyl-1,2-ethanediol or

1,6-bis(4-methoxyphenyl)-1,5-hexadiene-3,4-diol.

The compounds I possess organoteptic properties and therefore permit thedevelopment of methods useful in enhancing the flavor of foods. Thesecompounds are also useful in enhancing the odor, masking any unpleasantodor or enhancing the flavor of tobacco products.

These compounds may be used individually in an amount effective toenhance a characteristic flavor or odor of a given material. Thecompounds may also be mixed with other flavor or fragrance components inan amount sufficient to provide the desired flavor or odorcharacteristic.

The amount required to produce the desired, overall effect variesdepending upon the particular compound chosen, the product in which itwill be used, and the particular effect desired.

For example, depending upon the selection and concentration of thecompounds I used, addition of the compounds I either singly or as amixture to cigarette tobacco at levels ranging from about 5 ppm to about50,000 ppm tends to enhance the smoking flavor and/or mask undesirablesmoking odors. An important property of these compounds I is that theflavorant or odorant is covalently bound as an non-volatile compound andit is only when the tobacco product is ignited and burns that theflavorant or odorant is released.

Addition of the diols I of formula I either separately or as a mixtureat levels suitably ranging from about 5 ppm to about 50,000 ppm byweight onto the media enclosing the tobacco serves to incorporate theodorant/flavorant in the side-stream smoke as the tobacco product burns.Air borne flavorants and/or odorants along with other combustionproducts are thus introduced. This newly formed odorant or flavorantserves to enhance or mask the smoking odors depending upon selection anduse levels of the compounds I.

The diols I are also particularly useful in the flavoring andaromatizing of cooked foods. Addition of the diols either singly or as amixture to a cake batter, e.g. a microwave cake batter, serves to impartappropriate baking aromas to the cake as it is heated in the microwaveas well as impart flavoring in the finished product. Typically, diols Iare employed at levels ranging from about 0.0005 to about 10%, inparticular from 0.05 to about 5.00%.

In addition to the baking aromas, other pleasant organoleptic propertiesmay be provided, the palette is broad and may comprise depending on thecompound I used—floral, fruity, sweet, herbaceous, balsamic, spicy,cinnamon, woody, vanillin notes.

Notewortly are, furthermore, the stability of the novel flavorants.

A suitable temperature range may extend from about 70° C. to about 300°C., or even more.

The compounds I may be incorporated into the foodstuff or the smokingcomposition, e.g. the tobacco product along with other ingredients. Suchother ingredients include emulsifiers, carriers, binders, sweeteners,stabilizers, buffers and solvents, etc.

The addition of the diol I may generally be effected according tomethods known in the art, e.g. as such or dissolved in any suitablesolvent, e.g. in an alcohol, such as ethanol or aqueous ethanol, etc. Itmay then be sprayed or injected into the tobacco and/or tobaccosubstitute matrix. Such method ensures an even distribution of theflavorant additive throughout the filler, and thereby facilitates theproduction of a more uniform smoking composition. Alternatively, theflavorant may be incorporated as part of a concentrated tobacco extractwhich is applied to a fibrous tobacco web as in the manufacture ofreconstituted tobacco. Another suitable procedure is to incorporate theflavorant in tobacco or tobacco substitute filler in a concentrationbetween about 0.5-5 weight percent, based on the weight of filler, andthen subsequently to blend the treated filler with filler which does notcontain flavorant additive. Naturally, the additive can also be presentas a surface coating or absorbed component of the paper wrapper, and/orthe additive can be incorporated as a component of the adhesiveformulation which is utilized to seal the sideseam of cigarette paperwrappers.

The flavorant additive is released preferably during ignition andburning of the smoking composition, e.g. the tobacco product or duringthe baking or the microwaving process of the foodstuff.

A large number of the compounds I—actually the majority thereof—areknown. In as far as the novel compounds are concerned, the followingapplies:

Pinacol diols can be prepared from the corresponding aldehydes andketones by standard methods known to those skilled in the art—seeComprehensive Organic Synthesis, Barry M. Trost, ed., Vol. 3, 1991, pp563-579. For example, reaction of aldehydes or ketones with metals—e.g.Zn, Mg, Ce, Al(Hg) or Ti—and acid—e.g. acetic acid—provides pinacoldiols I. Various aldehydes and ketones can also be transformed byelectrochemical means to their pinacol diols. Pinacol diols can also beprepared by reduction of benzoins. All these methods are outlined by B.M. Trost.

Two compounds of this invention are novel, i.e. 1,6-bis(4-methoxyphenyl)-1,5-hexadiene-3,4-diol and2,5-dihexyl-1,6-diphenyl-1,5-hexadiene-3,4-diol. These may be obtainedby subjecting 1,4-methoxycinnamaldehyde or α-hexylcinnamaldehyde topinacolisation as outlined above.

The following examples are set forth herein to illustrate methods ofsynthesis of the pinacol diol derivatives I and their use as flavorantsand flavor precursors. These examples are intended only to illustratethe embodiments of this invention and are in no way meant to limit thescope thereof.

All parts, proportions, percentages and ratios used herein are by weightunless otherwise indicated.

EXAMPLE 1 1,6-Diphenyl-1,5-hexadiene-3,4-diol

A mixture of cinnamaldehyde (200 g, 1,5 mol), zinc (98.9 g, 1,5 mol),water (380 ml), and ether (230 ml) was heated to reflux under a nitrogenatmosphere. Acetic acid (175 ml) was added over a 2 hour period. Thereaction was heated at reflux for an additional 3 hours. The mixture wascooled and filtered. Ethyl acetate and ether (1:2) were added and themixture was washed sequentially with water (2×), aqueous sodiumbicarbonate solution until neutral, brine, and dried over sodiumsulfate, filtered, and the solvent was evaporated under reducedpressure. The syrup obtained was crystallized from ethyl acetate to givemeso-1,6-diphenyl-1,5-hexadiene-3,4-diol.

mp: 150-152° C., ¹H-NMR (CDCl₃) d 7.42-7.20 (10 H, m), 6.71 (2 H, d,J=15.87 Hz), 6.29 (2 H, dd, J=6.41 and 15.87 Hz), 4.49-4.39 (2 H, m),2.24 (2 H. OH). IR (KBr) 3298, 2908, 1449, 963, 746 cm-¹. MS m/e (%abundance) 266 (1), 133 (100), 115 (22), 77 (25), 55 (67).d,1-1,6-Diphenyl-1,5-hexadiene-3,4-diol can be isolated from thereaction mixture.

¹H-NMR (CDCl₃) d 7.42-7.20 (10 H, m), 6.72 (2 H, d, J=16.17 Hz),6.34-6.18 (2 H, m), 4.32-4.24 (2 H, m), 2.55 (2 H, s). IR (KBr) 3313,1449, 1047, 970, 690 cm⁻¹. MS m/e (% abundance) 266 (1), 133 (100), 115(25), 55 (29).

EXAMPLE 2 1,6-Bis(4-methoxyphenyl)-1,5-hexadiene-3,4-diol

In a fashion similar to that described in Example1,1,4-methoxycinnamaldehyde was treated with zinc and acetic acid toprovide 1,6-bis(4-methoxyphenyl)-1,5-hexadiene-3,4-diol.

mp: 145-146° C. ¹H-NMR (CDCl₃) d7.34-7.28 (4 H, m), 6.86-6.61 (4 H, m),6.69-6.59 (2 H, m), 6.29-6.06 (2 H, m), 3.80 (6 H, s). IR (KBr) 3365,2956, 2838, 1606, 1512, 1252, 1031 cm-¹. MS m/e (% abundance) 326 (1),163 (100), 55 (18).

EXAMPLE 3 2,5-Dihexyl-1,6-diphenyl-1,5-hexadiene-3,4-diol

In a fashion similar to that described in Example 1,α-hexyl-cinnamaldehyde was treated with zinc and acetic acid to provide2,5-dihexyl-1,6-diphenyl-1,5-hexadiene-3,4-diol.

mp: 86-86.5, ¹H-NMR (CDCl₃) d 7.38-7.16 (10 H, m), 6.73 (2 H, bs), 4.33(2 H, bs), 2.56-2.46 (4 H, m), 2.14-2.06 (2 H, m), 1.60-1.49 (4 H, m),1.40-1.21 (10 H, m), 0.90-0.84 (6 H, m). IR (KBr) 3455, 3296, 2922,2853, 1454, 1091, 699 cm⁻¹. MS m/e (% abundance) 434 (3), 218 (46), 217(100), 91 (22).

EXAMPLE 4 Preparation of an α-hexylcinnamaldehyde Cigarette

An ethyl acetate solution of the compound from Example 3 was applied tocigarette papers at the rate of 1000 ppm. (Application rates of 5 to50,000 ppm may actually be useful). The paper was incorporated intocigarettes. Prior to smoking, no odor of α-hexylcinnamaldehyde wasobserved. Upon smoking, a noticeable and persistent floral odor wasobserved in the room air. The floral odor was, actually, alreadyobserved on first puff.

EXAMPLE 5 Preparation of a Vanillin Cigarette

An alcohol/water solution of the compound1,2-bis(4-hydroxy-3-methoxyphenyl)-1,2-ethanediol was applied tocigarette papers at the rate of 500 ppm. The paper was incorporated intocigarettes. Prior to smoking, no odor of vanillin was observed. Uponsmoking a faint, but distinct odor of vanillin was observed in the roomair.

What is claimed is:
 1. A foodstuff containing an organoleptically effective amount of a flavorant-release additive, the flavorant-release additive being a 1,2 diol of the formula

wherein R¹ is one of the radicals

where R² is H, lower alkyl R³, R⁴ are H, lower alkyl, lower alkoxy, hydroxy, or R³+R⁴ together are methylenedioxy, R⁵ is lower alkyl and the broken lines represent in the ring one additional bond and in the side chain an optional bond.
 2. The foodstuff according to claim 1, wherein the foodstuff is a bakeable foodstuff.
 3. The foodstuff according to claim 2, wherein the concentration of the flavorant—release additive is about 0.0005 to about 10%, preferably about 0.005 to about 5% w/w.
 4. The foodstuff according to claim 2, wherein R³ and R⁴ in the formula Ia) diol is hydrogen.
 5. The foodstuff according to claim 2, wherein R² is hydrogen.
 6. The foodstuff according to claim 2, wherein R² in the formula Ib) diol is methyl.
 7. The foodstuff according to claim 2, wherein R² in the formula Ic) diol is methyl and there is an optional bond in the side chain of the molecule.
 8. The foodstuff according to claim 2, wherein the compound of Formula I is selected from the group consisting of 1,6-diphenyl-1,5-hexadiene-3,4-diol, 3,4-dimethyl-1,6-bis(2,6,6-trimethyl-1-cyclohexen-1-yl)-1,5-hexadiene-3,4-diol, 3,4-dimethyl-1,6-bis(2,6,6-trimethyl-2-cyclohexen-1-yl)-1,5-hexadiene-3,4-diol, 1,2-bis(4-hydroxy-3-methoxyphenyl)-1,2-ethanediol, 1,2-bis(1,3-benzodioxol-5-yl)-1,2-ethanediol, 1,2-bis(4-methoxyphenyl)-1,2-ethanediol, 1,2-diphenyl-1,2-ethanediol, 1,6-bis(4-methoxyphenyl)-1,5-hexadiene-3,4-diol and 2,5-dihexyl-1,6-diphenyl-1,5-hexadiene-3,4-diol.
 9. The foodstuff according to claim 1, wherein the foodstuff is a microwaveable foodstuff.
 10. The foodstuff according to claim 9, wherein the concentration of the flavorant—release additive is about 0.0005 to about 10%, preferably about 0.005 to about 5% w/w.
 11. The foodstuff according to claim 9, wherein R³ and R⁴ in the formula Ia) diol is hydrogen.
 12. The foodstuff according to claim 9, wherein R² is hydrogen.
 13. The foodstuff according to claim 9, wherein R² in the formula Ib) diol is methyl.
 14. The foodstuff according to claim 9, wherein R² in the formula Ic) diol is methyl and there is an optional bond in the side chain of the molecule.
 15. The foodstuff according to claim 9, wherein the compound of Formula I is selected from the group consisting of 1,6-diphenyl-1,5-hexadiene-3,4-diol, 3,4-dimethyl-1,6-bis(2,6,6-trimethyl-1-cyclohexen-1-yl)-1,5-hexadiene-3,4-diol, 3,4-dimethyl-1,6-bis(2,6,6-trimethyl-2-cyclohexen-1-yl)-1,5-hexadiene-3,4-diol, 1,2-bis(4-hydroxy-3-methoxyphenyl)-1,2-ethanediol, 1,2-bis(1,3-benzodioxol-5-yl)-1,2-ethanediol, 1,2-bis(4-methoxyphenyl)-1,2-ethanediol, 1,2-diphenyl-1,2-ethanediol, 1,6-bis(4-methoxyphenyl)-1,5-hexadiene-3,4-diol and 2,5-dihexyl-1,6-diphenyl-1,5-hexadiene-3,4-diol.
 16. The foodstuff according to claim 1, wherein the concentration of the flavorant—release additive is about 0.0005 to about 10%, preferably about 0.005 to about 5% w/w.
 17. The foodstuff according to claim 1, wherein the compound of Formula I is selected from the group consisting of 1,6-diphenyl-1,5-hexadiene-3,4-diol, 3,4-dimethyl-1,6-bis(2,6,6-trimethyl-1-cyclohexen-1-yl)-1,5-hexadiene-3,4-diol, 3,4-dimethyl-1,6-bis(2,6,6-trimethyl-2-cyclohexen-1-yl)-1,5-hexadiene-3,4-diol, 1,2-bis(4-hydroxy-3-methoxyphenyl)-1,2-ethanediol, 1,2-bis(1,3-benzodioxol-5-yl)-1,2-ethanediol, 1,2-bis(4-methoxyphenyl)-1,2-ethanediol, 1,2-diphenyl-1,2-ethanediol, 1,6-bis(4-methoxyphenyl)-1,5-hexadiene-3,4-diol and 2,5-dihexyl-1,6-diphenyl-1,5-hexadiene-3,4-diol.
 18. The foodstuff according to claim 1, wherein R³ and R⁴ in the formula Ia) diol is hydrogen.
 19. The foodstuff according to claim 1, wherein R² is hydrogen.
 20. The foodstuff according to claim 1, wherein R² in the formula Ib) diol is methyl.
 21. The foodstuff according to claim 1, wherein R² in the formula Ic) diol is methyl and there is an optional bond in the side chain of the molecule.
 22. A method of flavoring a food, comprising treating the food with an organoleptically effective amount of a 1,2-diol of the formula

wherein R¹ is one of the radicals

where R² is H, lower alkyl R³, R⁴ are H, lower alkyl, lower alkoxy, hydroxy, or R³+R⁴ together are methylenedioxy, R⁵ is lower alkyl and the broken lines represent in the ring one additional bond and in the side chain an optional bond.
 23. A method of flavoring a finished food, comprising baking or microwaving a food containing an organoleptically effective amount of a 1,2-diol of the formula

wherein R¹ is one of the radicals

where R² is H, lower alkyl R³, R⁴ are H, lower alkyl, lower alkoxy, hydroxy, or R³+R⁴ together are methylenedioxy, R⁵ is lower alkyl and the broken lines represent in the ring one additional bond and in the side chain an optional bond.
 24. The method according to claim 23, wherein the 1,2 diol of Formula I is selected from the group consisting of 1,6-diphenyl-1,5-hexadiene-3,4-diol, 3,4-dimethyl-1,6-bis(2,6,6-trimethyl-1-cyclohexen-1-yl)-1,5-hexadiene-3,4-diol, 3,4-dimethyl-1,6-bis(2,6,6-trimethyl-2-cyclohexen-1-yl)-1,5-hexadiene-3,4-diol, 1,2-bis(4-hydroxy-3-methoxyphenyl)-1,2-ethanediol, 1,2-bis(1,3-benzodioxol-5-yl)-1,2-ethanediol, 1,2-bis(4-methoxyphenyl)-1,2-ethanediol, 1,2-diphenyl-1,2-ethanediol, 1,6-bis(4-methoxyphenyl)-1,5-hexadiene-3,4-diol and 2,5-dihexyl-1,6-diphenyl-1,5-hexadiene-3,4-diol. 